Insecticidal and fungicidal use of n-aryl dithiooxamides



United States Patent O 3,422,202 INSECTICIDAL AND FUNGICIDAL USE OF N-ARYL DITHIOOXAMIDES John F. Olin, Ballwin, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Original application Feb. 3, 1964, Ser. No. 342,247, now Patent No. 3,318,675, dated May 9, 1967. Divided and this application Feb. 20, 1967, Ser. No. 617,080 U.S. Cl. 424328 12 Claims Int. Cl. Atllm 9/12 ABSTRACT OF THE DISCLOSURE N-aryl dithiooxamides are useful as pesticides, specifically as insecticides and fungicides.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a division of my copending application Ser. No. 342,247, filed Feb. 3, 1964, now U.S. Patent No. 3,318,675.

BACKGROUND OF THE INVENTION This invention comprises the pesticidal use of certain carbocyclic compounds. Specifically, compounds of the formula v where R is hydrogen, hydroxy or nitro or monovalent aliphatic hydrocarbon or hydrocarbonoxy having up to four carbon atoms, where R and R" are hydrogen, hydroxy, halogen or nitro or monovalent hydrocarbon or hydrocarbonoxy having up to four carbon atoms; and where X is hydrogen or halogen, are useful as herbicides, insecticides, fungicides or combinations thereof.

When insecticidal activity is desired, the above class of compounds is further limited to compounds of the same formula but where the substituent characters are as follows:

R is hydrogen, hydroxy, or nitro or monovalent aliphatic hydrocarbon or hydrocarbonoxy having up to four carbon atoms; where R and R" are hydrogen, halogen or nitro or monovalent aliphatic hydrocarbon having up to four carbon atoms; and where X is hydrogen or halogen, provided that at least one of the R, R, R or X radicals is not hydrogen.

DESCRIPTION OF THE PRIOR ART In recent years, the use of chemicals for controlling various biological forms has found widespread acceptance. This is especially true among agriculturalists interested in controlling plant systems and insect pests. For example, chemical compositions have previously been applied to the soil or to the foliage of fully developed plants, thereby destroying certain types of plants in a selective manner and allowing others to continue their growth in a more favorable environment. This type of control, enabling certain plants to grow freely, unhampered by competing noxious plants, has also been achieved by the application of chemical compositions to the soil, which chemical compositions either prevent germination of undesirable seeds or destroy the emerging seedlings immediately after germination. Other dangers confronting plant growth and crop yields occur in the form of insect pests and plant diseases. These threats to desirable plant life have been lessened by the application of herbicides, insecticides and fungicides to the soil, foliage of plants, and surrounding atmosphere.

Very effective control and protection of desirable plant life is therefore possible through the use of chemicals formulated to provide protection as selective herbicides, insecticides, and plant fungicides. However, all requirements for effectiveness and selectivity among pesticides have not been satisfied. There are still many demands to satisfy, either for more effective pesticides with a greater selectivity than an old pesticide, or for pesticides with a different selectivity. A few N-aryl dithiooxarnides have been synthesized but their pesticidall activity has not been recognized prior to the instant discovery.

SUMMARY It is a primary object of this invention to provide compositions for killing insects active on foliar contact. It is a further primary object of this invention to provide methods for the selective destruction of undesirable insect life. It is another object to provide a process for killing insects which may be harmful to plant growth. It is yet another object to provide methods for protecting plant growth from fungi. It is another object to provide methods for controlling pests. Additional objects, benefits, and advantages will become apparent as the detailed description of the invention proceeds.

The compounds useful in the practice of the present invention are those having the molecular configuration:

R RI NHOCNH2 Where R is hydrogen, hydroxy, or nitro or monovalent aliphatic hydrocarbon or hydrocarbonoxy having up to four carbon atoms; where R' and R" are hydrogen, hydroxy, halogen or nitro or monovalent aliphatic hydrocarbon or hydrocarbonoxy having up to four carbon atoms; and where X is hydrogen or halogen.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The N-aryl dithooxarnides useful in the practice of this invention can contain an unsubstituted phenyl group attached to the nitrogen atom, as for example, N-phenyl dithiooxamide. Also included are compounds having substituents on the aromatic ring in either the ortho, meta or para position. Furthermore, combinations of ortho and meta, ortho and para, meta and para, di-meta, and ortho, meta and para substitutions are within the scope of this invention.

Substitutions on the ring can range to as high as four substituents, the type of substituents being limited as characterized in the above generic formula. These substitutions on the ring can consist of halogen radicals, particularly chlorine, of nitro radicals, of hydroxyl radicals and of aliphatic hydrocarbyl and aliphatic hydrocarbyloxy radicals having up to four carbon atoms. Compounds illustrative of these many possible substitutions include N-(Z-methoxy 3,4 dichloro 6 ethylphenyl)dithioox-amide, N-(2-allyl-3,4-dichlorophenyl)dithiooxamide, N (2,4 dibromo 3 hydroxy-6-vinylphenyl)dithiooxamide, N (2,4,5 tr-ichlorophenyDdithiooXarnide, N (4- isopropylphenyl)dithiooxamide, N-(2-chloro 3 nitro-4- ethoxyphenyl)dithiooxamide, N-(2-chloro-4-vinylphenyl) dithiooxamide, N-(2-methoxy-3-nitro 5 chlorophenyl) dithiooxamide, N-(B-nitro 4 tertbutylphenyl)dithiooxamide, and N-(2-methyl-3,4-dibromophenyl)dithiooxamide.

Compounds included within the above formula which are preferred for use in this invention are compounds of the formula where R is a hydrogen radical or an alkyl radical having up to four carbon atoms; and where R is a hydrogen or chloro radical or an alkyl radical having up to four carbon atoms.

Examples of preferred dithiooxamides include N-(3- chlorophenyl) dithiooxamide, N- 3-chloro-4-ethylphenyl) dithiooxamide, N- (5-chloro-3,4-dirnethylphenyl) dithiooxamide, N-(2,4 dichlorophenyl)dithiooxamide, and N-(3,4- dichloro-5-tert-butylphenyl) dithiooxamide.

Compounds of this invention are useful as pesticides. One distinctive utility of the compounds is their insecticidal activity. In addition, the compounds are also herbicidally active; many are active fungicides. Some of the compounds possess multiple activity in two or more of the above mentioned areas. Hence, the user can benefit from the application of these compounds in a dual or multiple manner, depending upon which compound or mixture of compounds is selected.

The dithiooxamides of this invention are prepared by reacting the appropriately substituted phenyl isothiocyanate with a cyanide to produce a thiooxanilonitrile. The thiooxanilonitrile is then reacted with hydrogen sulfide to produce the corresponding dithiooxamide. The synthesis is more fully described in Reissert and Bruggemann, Ber., 57, 982 (1924).

The advantages and benefits of the present invention will become more fully understood when interpreted in view of the detailed description set forth in the following examples.

Example 1 A quantity of 45 grams of 2-ethoxyphenyl isothiocyanate, 135 grams of 1,2-di1nethoxyethane, 18 grams of potassium cyanide, and 150 ml. of water were mixed together and stirred until the isothiocyanate dissolved. The amber solution was filtered and the filtrate diluted with 600 ml. of water. The filtrate was acidified with HCl, causing an orange liquid to separate and solidify. This solid, identified as 2-ethoxythiooxanilonitrile, was filtered and air-dried. Upon crystallization from hexane, the melting point was 75-76 C. Analysis of the crude product was: :58.29 and 58.27%, H:5.10 and 4.98%, 8:15.12 and 15.30%; calculated for C H N OS:C=58.24% H:5.24% S: 15.54%

A quantity of 27 grams of 2-ethoxythiooxanilonitrile and 100 ml. of 20% ammonium sulfide solution were mixed in the presence of about 50 ml. of methanol. Upon standing overnight, a crystalline precipitate separated. The crystals were filtered, washed with water, and air-dried. Upon recrystallization from a heptane-toluene mixture, the product, identified as N-(2-ethoxyphenyl)- dithiooxamide, had a melting point of 108-l1l C. Analysis of the product was: C:50.43 and 50.48%, H:5.37 and 5.32%, 8:26.19 and 26.08%; calculated for C H N OS :C:49.97%, H:5.03%, S:26.68%.

Following the procedure described in Example 1, several other dithiooxamides were prepared from the corresponding aromatic isothiocyanate. They are as follows:

(2) N- Z-tert-butylphenyl) dithiooxamide (3) N- Z-tert-b utyl--chloro-6-methylphenyl) dithiooxamide (4) N-4-tert-butylphenyl)dithiooxamide (5 N-(3-chloro-4-methoxyphenyl) dithiooxamide (6 N- 2,4-dimethoxyphenyl -dithiooxamide (7) N- 3,4-dichlorophenyl) dithiooxamide (8) N- 5 -chloro-2-methoxyphenyl) dithiooxamide (9) N- (2,4-ditert-butylphenyl) dithiooxamide 4 10) N- (4-tert-butyl-2-methylphenyl dithiooxamide 1 1 N-(5-chloro-2,4-ditert-butyl-6-methylpl1enyl) dithiooxamide l 2) N- 2-tert-butyl-4-methylphenyl) dithiooxamide 13) N- 2,5-dimethoxyphenyl dithiooxamide 14) N- 2-tert-butyl-6-metl1ylphenyl) dithiooxamide 15) N-phenyl dithiooxamide l 6) N- 4-tert-butyl-2,6-diethylphenyl) dithiooxamide 17) N- 2-chlorophenyl) dithiooxamide l 8) N- 3 -chlorophenyl) dithiooxamide 19) N-(4-chlorophenyl) dithiooxamide (20) N- 3-chloro-2-methylphenyl) dithiooxamide.

Melting points and elemental analyses for the prepared compounds are as follows:

TABLE I Melting Point, Elemental Analysis, percent wt. Example C.

Calculated Found H=6. 39 I-I=6. 47 s=25. 41 s=25. 10 3 -101 C=58. 52 C=59. 52

H=5. 67 H=5. 99 s=12.02 s=11.2s 4 111-114 s=25. 41 s=24. 70 5 167-170 s =23.1s 5 =23. 50 6 148-154 s=25. 02 s=25. 05 -162 0:36. 23 o=36. 21

H =2. 28 H =2. 34 s=24. 10 s=2as5 143-146 s =24. 59 s =24. 23 129-130 s =20. 79 s =20. 63 118-120 s =24. 07 s =23. 02 179180 s=17. 90 s=17. 43 139-140 s =24. 07 s =23. 98 135-137 s=25. 02 s=24.s1 -176 s =24. 07 s =24. 24

97-98 115-116 s =20. 79 s =20. 79 139-140 s =27. 79 s =28. 00 130-131 s =27. 79 s =27. 93 -181 s =27. 79 s =27. 71 138-139 0:14. 16 0 14.11

H=3.71 H=3.75 s=26.20 s=26. 09

A tube was filled with 50 ml. of distilled water. To this was added a sufiicient quantity of a 1% solution of the appropriate dithiooxamide in acetone to bring the concentration of dithiooxamide to the desired level. Approximately 25 yellow fever mosquito larvae, Aedes aegypti, were transferred to the tube where they remained at room temperature for 24 hours, after which time mortality observations were measured and recorded.

Insecticidal activity on armyworm larvae was determined according to the following procedure. Ten leaf discs 4 inch in diameter from an uninfested Woods prolific lima bean plant were treated with one microliter of an acetone solution containing a specified number of micrograms of the appropriate dithiooxamide. One second instar southern armyworm larva, Prodem'a eria'ania, was placed beside each leaf disc. The larva and disc were then enclosed within a plastic cap for 48 hours at room temperature, after which time mortality observations were measured and recorded. Results are reported below in Table II. The figures listed under the tested larvae indicate the mortality rate at the specified concentration of use.

TABLE 11 Sample Aedes aegypti Prodenia cridam'a 1 100% at 10 p.p.m 2 90% at 10 p.p.m 100% at 20 pg. 3 .{l00% at 10 p.p.m 100% at 20 pg. 90% at 2 p.p.m 100% at 10 pg.

100% at 1 pg. 4 100% at 10 p.p.m 5 100% at 10 p.p.m 7... 100% at 10 p.p.m 60% at. 10 pg. 8 100% at 10 ppm .{60% at 10 g. 9 30% at 10 pg. 10 50% at 10 p.p.m 30% at 10 pg. 11 {100% at 10 g. 100% at 1 pg. 12 90% at 10 p.p.m

90% at 10 p.p.m 100% at 10 pg. 50% at 10 ppm 60% at 10 g. 100% at 10 p.p.m.

100% at 10 p p m 70% at 10 pg. 100% at 10 p.p.m 60% at 10 pg.

60% at 10 p.p.m 100% at 10 g.

In contrast, compounds Nos. 6, 13 and 15, although active herbicides, exhibited very little or no insecticidal activity.

Certain N-aryl dithiooxamides also exhibit activity as plant and soil fungicides. For example, N-phenyldithiooxamide is active as a soil fungicide against the organisms Rhizoctonia solani and Pythz'um' ultimum at a concentration of 30 p.p.m. It is also active as a wheat rust eradicant at a concentration of 0.3%. In addition, N-(2-ethoxyphenyl) dithiooxamide, N- 2-tert-butylphenyl) dithiooxamide, N-(4-tert-butylphenyl)dithiooxamide, N-(S-chloro- Z-methoxyphenyl) dithiooxamide, N- 3-chloro-4-methoxyphenyl)dithiooxamide, N (4-tert-butyl-2,6-diethylphenyl)dithiooxamide, N-(2-chlorophenyl)dithiooxamide, N- (3-chlorophenyl)dithiooxamide, N (4-chlorophenyl)dithiooxamide, N (3-chloro-2-methylphenyl)-dithiooxamide, and N-(3,4-dichlorophenyl)dithiooxamide are fungicidally active against apple scab, Venturia inaequalis, at a concentration of p.p.m.

The pesticidally active compounds of this invention are either solid or liquid materials, depending upon the particular substituents present in the compounds. To aid in achieving a uniform distribution of the active compounds over the entire area of the soil or plants to be treated, it is often advantageous to employ a composition comprising a diluent or extending agent in addition to the actual compounds. Suitable solid extending agents are those which render the compositions permanently dry and free-flowing. Therefore, hygroscopi materials are not preferred extending agents unless there is included in the composition a separate substance to aid flowability. Effective solid diluents include natural clays, such as china clays, bentonites, and the attapulgites; other minerals in their natural state such as talc, pyrophylite, quartz, diatomaceous earth, fullers earth, chalk, rock phosphate, and sulfur; and chemically modified minerals, such as acid-washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, and colloidal silica. These diluents may represent a substantial portion, e.g. 50 to 98% by weight, of the entire formulation as applied to plant or soil. Formulations more concentrated with respect to the active ingredient may be prepared but they will usually require additional dilution by the user in order to properly prepare the composition for the most effective usage. Therefore the toxicant formulation as applied in the field will normally consist of a minor amount, i.e. less than 50% by weight of the entire formulation, of the N-aryl dithiooxamides and a major amount, or more than 50% of the entire formulation, of an adjuvant or adjuvants.

Liquid extending agents are also useful in the practice of this invention. The N-aryl dithiooxamides of this inven tion are insoluble in water and are readily soluble in most organic solvents. Therefore the choice of a liquid extending agent is quite variable if a solution of the active ingredients is desired. In addition, the active compounds need not be dissolved but merely dispersed in the extending agent in the form of a suspension or emulsion. One method of forming this dispersion is to dissolve the N- aryl dithiooxamides in a suitable organic solvent and then add this solution to water or some other liquid extending agent to form the dispersion. Examples of some organic solvents suitable for use as extending agents when a solution is desired include: alcohols such as ethyl, isopropyl, N-propyl, and butyl alcohols; ketones such as acetones, methylethyl ketones, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene. Solvents useful as extending agents when a dispersion of the active compound in the solvent is acceptable include: water, hexane, and other aliphatic hydrocarbons.

The incorporation of a surface active agent into the herbicidal formulation is an aid helpful in forming uniform dispersions or emulsions of the active N-aryl dithiooxamides in water. The surface active agent, that is the Wetting, emulsifying, or dispersion agent, may be either anionic, cationic, non-ionic, or mixtures thereof. Suitable wetting agents are the organic compounds capable of lowering the surface tension of water and include the conventional soaps such as the water-soluble salts of long-chain carboxylic acids; the amino soaps, such as the amine salts of long-chain carboxylic acids; the sulfonated animal, vegetable and mineral oils; quaternary salts of high molecular weight acids; rosin soaps such as salts of abietic acid; sulfuric acid salts of high molecular weight organic compounds; algin soaps; and simple and polymeric compositions having both hydrophobic and hydrophilic functions.

The concentrated compositions of this invention ordinarily have the active ingredient in the surface active agent present in higher concentrations than the toxicant compositions applied in the field, so that upon dilution with an extending agent, compositions containing optimum proportions of active ingredient and surface active agent are prepared to obtain uniform distribution and to maintain the active ingredients in a form enabling prompt assimilation by the plants.

The concentrate compositions of this invention preferably comprise 5% to by weight of the active ingredient, the remainder consisting of the adjuvant. If a liquid concentrate is desired, this adjuvant may be solely liquid extending agent or surface active agent, but preferably is a combination of the two. Preferably the surface active agent comprises from 0.1% to 15% of the concentrate, and the liquid extender comprises from 5% to 95% of the concentrate. If a solid concentrate is desired, the adjuvant is usually made up solely of a solid extender unless the dust concentrate is to be applied as a wettable powder, in which case an amount of surface active agent comparable to that used in the liquid formulation, that is 0.1% to 15%, may be desirable.

Carrier materials or diluents necessary to dilute the concentrates to a toxicological level suitable for plant control can be either a liquid or particulate solid. Materials mentioned previously as extenders can also be used as carriers; however the use of some of these materials as carriers is often not economically feasible. Water is a preferred liquid carrier; suitable solid carriers include solid fertilizers such as ammonium nitrate, urea, and super phosphate, as well as other materials in which plant organisrns may take root and grow, such as compost, manure, humus and sand. 7

In addition to the above described conditioning agents, other adjuvants may be added, such as insecticides, fungicides, nematocides and other herbicides of a supplementary nature. This may be done when it is desired to broaden the spectrum of activity to include other problem Weeds, insects or fungi.

The compositions of this invention are applied to the plant system or to the area to be controlled in a conventional manner. Thus, the dust and liquid compositions may be applied to the foliage of growing plants or to the soil by the use of power-operated clusters and sprayers as well as manually operated devices. Some of the com pounds of this invention provide superior protection and control when mixed with the top few inches of soil. This can be accomplished by addition of the composition to irrigation water supplied to the field to be heated. Dust compositions sprinkled on the surface of the soil can be distributed below the surface 'by the usual discing, dragging or mixing operations.

The application of a toxic amount of the N-aryl dithiooxamides to the area to be controlled is essential to the practice of this invention. The exact dosage to be applied is dependent not only upon the specific dithiooxamide but also upon the particular type of protection desired. As a general rule, insecticidal activity of the N-aryl dithiooxamides is usually achieved by application of the N-aryl dithiooxamides in solutions or dispersions containing from 0.1% or less up to 10% or more by weight of the insecticidally active dithiooxamide. However, lower rates of application may be required with some of the dithiooxamides, particularly if a selective activity is desired, and higher rates may be required if it is desirable to include a fungicidally toxic amount of the dithiooxamide in the formulation.

The pesticidally active compounds of this invention have been described in terms of specific groups or types of N-aryl dithiooxamides. However, it should be noted that this invention is intended to cover those compounds in which the substituent groups (the R, R, R", and X radicals) can also contain constituents other than those mentioned it these constituents do not interfere with the biological activity of the parent N-aryl dithiooxamide. Those skilled in the art will recognize that a compound containing a hydrocarbon radical that is substituted with a non-interfering group is the equivalent of the corresponding compound containing a non-substituted hydrocarbon radical. Such a non-interfering group can be initially present in a compound subject to one of the reactions of this invention and can, depending upon circumstances, either be retained in the product molecule or be destroyed or changed during the reaction; or such group can be introduced by known means into one of the new compounds of this invention subsequent to the formation of such compound. Accordingly, these and other modifications are contemplated which can be made without departing from the spirit of the described invention.

What is claimed is:

1. A method for inhibiting insect or fungal pests comprising applying to an area to be controlled a pesticidally effective amount of a compound of the formula where R is'slected from the group consisting of hydrogen, hydroxyl, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, R and R" are selected from the group consisting of hydrogen, hydroxyl, halogen, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, and X is selected from the group consisting of hydrogen and halogen.

2. A method according to claim 1 wherein said compound is N-(2-tert-butyl-5-chloro--6-methyl phenyl) dithiooxamide.

3. A method according to claim 1 wherein said compound is N-(3,4-dichlorophenyl)dithiooxamide.

4. A method according to claim 1 wherein said compound is N-(3-chloro-2-methyl phcnyl)dithiooxamide.

5. A method according to claim 1 wherein said compound is N-(5-chloro-2,4-ditert-butyl-6-methyl phenyl)dithiooxamide.

6. A method for inhibiting insect pests comprising applying to an area to be controlled an insecticidally effective amount of a compound of the formula where R is selected from the group consisting of hydrogen, hydroxyl, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, R and R are selected from the group consisting of hydrogen, hydroxyl, halogen, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, and X is selected from the group consisting of hydrogen and halogen.

7. A method according to claim 6 wherein said compound is an N-(alkyl-halophenyl)dithiooxamide.

8. A method according to claim 6 wherein said compound is an N-(monoalkyl-monohalophenyl)dithiooxamide.

9. A method according to claim 6 wherein said compound is N-(Z-methyl-S-chlorophenyl) dithiooxamide.

10. A method according to claim 6 wherein said compound is N-(2-tert-butyl-5-chloro-6-methylphenyl)dithiooxamide.

11. A method according to claim 6 wherein said compound is N-(Z-ditert-butyl-S-chloro 6 methylphenyl)dithiooxamide.

12. A method for inhibiting fungal pests comprising applying to an area to be controlled a fungicidally etfective amount of the compound of the formula where R is selected from the group consisting of hydrogen, hydroxyl, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, R and R" are selected from the group consisting of hydrogen, hydroxyl, halogen, and nitro, and aliphatic hydrocarbyl and aliphatic hydrocarbyloxy having up to 4 carbon atoms, and X is selected from the group consiting of hydrogen and halogen.

References Cited UNITED STATES PATENTS 2,732,401 1/1956 De La Mater 260-551 2,772,309 11/ 1956 Doerner 260551 2,837,417 6/1958 Fisher 71-2.7 2,941,879 6/1960 Goodhue 712.7

OTHER REFERENCES Grabendo et al., Chemical Abstracts, vol. 56, column lOO26(h), 1962.

Kumelj et al., Chemical Abstracts, vol. 56, column 22426(h), 1960.

ALBERT T. MEYERS, Primary Examiner.

R. S. DORCAS, Assistant Examiner.

U.S. Cl. X.R. 167-31; 71-98 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,422 ,202 Dated January 14 1969 Inventor(s) John F. Olin It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 71, "N- i-tert-butylphenyl)" should be N- (u-tert-buc l nen l) Column 8, line 20, "N-(Q-ditertbutyl-5-chloro" should be N-(2,4-ditert-butyl-5-chloro and line 40, "coneiting" should be --cons1st1ng SIGNED AND SEALED FEB 2 4 1970 M Atlanta "mil-Flotilla, It.

WILIIIML 3. 5m, JR. AllesfingOfficor Oomiasionar of Patents 

